JPH1124215A - Photosensitive silver halide color multilayer photographic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the photosensitive silver halide color photographic material capable of obtaining low graininess and high color purity and better intermediate image effect and at the same time restraining deterioration of sensitivity to minimum in whatever layers. SOLUTION: This photographic material is provided with at least a silver halide emulsion layer containing a yellow dye-forming DIR coupler combined with a 1,2,4-triazolyl group at a coupling site and a yellow dye-forming malondiamide DIR coupler combined with a 4,7-dihalogen-2-benzotriazolyl group at a coupling site, and a support covered with this emulsion layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to two different DIRs which can release a development inhibitory compound upon reaction with an oxidation product of a developer in at least one blue photosensitive layer associated with a yellow dye-forming coupler. Release (Development I
nhibitor Releasing)] and a light-sensitive silver halide color photographic multilayer material containing a coupler.

[0002]

2. Description of the Related Art A photosensitive color photographic material utilizing a subtraction process for color reproduction is selectively sensitized to blue light, green light and red light, and reacts with a primary amine-based oxidized color developer. Associates with yellow, magenta and cyan dye forming couplers which form complementary colors;
It is known to form silver halide emulsion layers. For example, using an acylacetanilide based coupler to form a yellow colored image; using a pyrazolone, pyrazolotriazole, cyanoacetophenone or indazolone based coupler to form a magenta colored image; like phenol or naphthol A cyan colored image is formed using a suitable phenolic coupler.

[0003] Typically, light-sensitive color photographic materials include a non-diffusive coupler separately incorporated into each light-sensitive layer of the material (embedded coupler materials). As a result, the light-sensitive color photographic material generally contains a yellow coupler and mainly contains a blue-sensitive silver halide emulsion layer sensitive to blue light (substantially shorter than about 500 nm), a magenta coupler, and A green-sensitive silver halide emulsion layer sensitive to predominantly green light (substantially between about 500-600 nm), and predominantly red light containing cyan couplers (substantially longer than about 590 nm) And a red-sensitive silver halide emulsion layer that is sensitive to light.

In photosensitive color photographic materials, during development,
It is also known to incorporate compounds that can release a development inhibitor upon reaction with the oxidation products of the color developer.
A typical example of such a compound is a DIR coupler having a group that has development inhibiting properties when released from the coupler. Said groups are introduced at the coupling position of the coupler. Examples of DIR couplers are CR Barr, JR Rartl.
e) and PWWittu
m) Author, Photographic Science and Eng.
3, 74-80 (1969) and 214, 217 (1969)
No. 3,227,554; U.S. Pat. No. 3,615,5;
No. 06; No. 3,617,291; No. 3,701,783; No. 3,933,500; No. 4,095,984; No.
Nos. 4,146,396; 4,149,886 and 4,47
No. 7,563.

The purpose of DIR couplers is to reduce particle size, enhance image clarity (eg, in the same layer or in the same colored image) through internal layers or internal image effects,
And improving color reproducibility by means of an intermediate layer or intermediate image effect (ie in different layers or different colored images). However, the photosensitive emulsion layer using a DIR coupler usually causes an intermediate image effect mainly in a high density region of a negative image, but also has a low density region which greatly affects image characteristics such as color saturation and brightness. It is often desired to exert an intermediate image effect.

The concept of two or more different DIR compounds in a photosensitive material is described, for example, in US Pat. No. 4,015,988, which teaches the use of a DIR coupler in combination with a DIR hydroquinone compound. However,
This combination did not give good results due to the very low photosensitivity of the hydroquinone DRI compound. JP-A-51-113,625 describes the simultaneous use of mercapto-based compounds which release a development inhibitor, such as compounds having different coupling activities. JP-A-56-137,353
The publication describes the simultaneous use of development inhibitor releasing compounds, one having a "timing" group and the other having no "timing" group. DD Patent No.246,63
Publication No. 6 describes the use of a combination of two DIR compounds, one being a mobile compound and the other a non-mobile compound. U.S. Pat. No. 4,355,100 describes the simultaneous use of two development inhibitor releasing compounds, one with an amino group and one without an amino group.
U.S. Pat. No. 5,126,236 discloses that when reacted with a DIR compound or DIR precursor or an oxidized developer,
Combinations of compounds that release IR compounds are described.

[0007] However, all of the above publications describe a combination of at least two DIR compounds, but solve the problem of achieving a better intermediate image effect and a better particle size while also achieving a lower sensitivity reduction. Not something.

[0008] EP 747,763 discloses a DIR having a 1,2,4-triazolyl group bonded at the coupling position.
Yellow couplers are described and, during development,
For example, a 1,2,4-triazolyl group having a benzylthio substituent with a hydrolyzable alkoxy- or aryloxy-carbonyl group attached to the 1,2,4-triazolyl group is released.

[0009] In contrast, US Pat. No. 5,006,452 discloses that during development, an oxidation reaction with a developer causes 4,7-dihalogen.
A color photographic material containing a DIR coupler having a 2-benzotriazolyl group is described. U.S. Patent No.
No. 5,332,656 discloses a) a yellow dye-forming diketomethylene coupler having a 4,7-dihalogen-2-benzotriazolyl group at an active coupling position, wherein color development is performed from the active coupling position. And b) a yellow dye-forming alkoxybenzoyl-acetanilide coupler having a releaseable 3-hydantoin group attached to the active coupling site, providing a compound having development inhibiting properties when the group is released by the reaction. A color photographic material comprising a combination of is described.

[0010]

That is, an object of the present invention is to make it possible to obtain a higher inhibitory activity by adding a DIR coupler even in a medium-speed film and a low-speed film. Is to obtain a low particle size and a higher color purity in a low density region.
It is another object of the present invention to obtain better intermediate image effects while minimizing sensitivity loss in all layers.

[0011]

SUMMARY OF THE INVENTION The present invention is a light sensitive silver halide color photographic multilayer material comprising a support substrate coated with at least one blue light sensitive silver halide emulsion layer associated with a yellow dye forming coupler. A) a yellow dye-forming DIR coupler with a 1,2,4-triazolyl group attached at the coupling position; and b) a compound which exhibits development inhibiting properties when released from the coupling position during development. A photosensitive silver halide color photographic multilayer material containing both a yellow dye-forming malonic diamide DIR coupler having a 7,7-dihalogen-2-benzotriazolyl group at the coupling position. In the yellow dye-forming DIR coupler (a),
The 1,2,4-triazolyl group includes groups having a benzylthio substituent attached to the hydrolyzable alkoxy- or aryloxy-carbonyl group on the 1,2,4-triazolyl group. Said photosensitive silver halide color material comprising a combination of a yellow dye forming DIR coupler as described above, upon exposure and development, develops a lower grain size and higher color purity and minimizes speed reduction in all layers. Provide a suppressed color image.

In the coupling position used in the present invention,
The yellow dye forming DIR coupler (a) having a 2,4-triazolyl group is represented by the following formula (I).

Embedded image (Wherein, R ₁ is an alkyl group, an aryl group, or —NHR
_{5 represents a} group (where R ₅ represents an alkyl group or an aryl group); R ₂ represents an alkyl group or an aryl group; TIME represents a “timing” group; , R ₃ represents an alkyl group or a phenyl group, and R ₄ represents a hydrogen atom or an alkyl group. )

In the above formula (I), the alkyl group represented by R ₁ , R ₂ and R ₅ preferably has 1 to 18 carbon atoms and may be substituted or unsubstituted. Preferred substituents on the alkyl group include an alkoxy group, an aryloxy group, a cyano group, an amino group, an acylamino group, a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, and a heterocyclic group. Specific examples of useful alkyl groups are isopropyl, isobutyl, tert-butyl, isoamyl, tert-amyl, 1,1-dimethylbutyl, 1,1-
Dimethylhexyl group, 1,1-diethylhexyl group, 1,1-dimethyl1-methoxyphenoxymethyl group, 1,1-dimethyl1-
An ethylthiomethyl group, a dodecyl group, a hexadecyl group, an octadecyl group, a cyclohexyl group, a 2-methoxyisopropyl group, a 2-phenoxyisopropyl group, an α-aminoisopropyl group, and an α-succinimidoisopropyl group.

In the formula (I), the aryl group represented by R ₁ , R ₂ and R ₅ preferably has a total of 6 to 35 carbon atoms, and particularly includes a substituted phenyl group and an unsubstituted phenyl group. . Preferred examples of the substituent in the aryl group include a halogen atom, a nitro group, a cyano group, a thiocyano group, a hydroxyl group and an alkoxy group (preferably having 1 to 15 carbon atoms such as a methoxy group, an isopropoxy group, an octyloxy group and the like). ), Aryloxy group (phenoxy group, nitrophenoxy group, etc.), alkyl group (preferably having 1 to 15 carbon atoms such as methyl group, ethyl group, dodecyl group, etc.), aryl group (preferably phenyl group, An amino group (for example, an unsubstituted amino group or an alkylamino group having 1 to 15 carbon atoms such as a diethylamino group or an octylamino group), a carboxyl group, An acyl group (preferably having 2 to 16 carbon atoms such as an acetyl group and a decanoyl group), an alkoxycarbonyl group (preferably methoxy group); A cyclocarbonyl group, a butoxycarbonyl group, an octyloxycarbonyl group, a dodecyloxycarbonyl group, an alkyl group such as a 2-methoxyethoxycarbonyl group having 1 to 20 carbon atoms, an aryloxycarbonyl group (preferably, A carboxy group such as a phenoxycarbonyl group or an alkyl group having 6 to 20 carbon atoms, such as a toluoxycarbonyl group;
Ethylcarbamoyl group, octylcarbamoyl group, etc.),
Acylamino group (preferably one having 2 to 21 carbon atoms such as acetamido group, octaneamido group, 2,4-ditert-pentylphenoxyacetamide group, etc.), sulfo group, alkylsulfonyl group (preferably methylsulfonyl group) , An octylsulfonyl group and the like having 1 to 15 carbon atoms), an arylsulfonyl group (preferably having a carbon number of 6 to 20 such as a phenylsulfonyl group and an octylphenylsulfonyl group), an alkoxysulfonyl group (preferably Is a group having 1 to 15 carbon atoms such as methoxysulfonyl group and octyloxysulfonyl group, an aryloxysulfonyl group (preferably having 6 to 20 carbon atoms such as phenoxysulfonyl and the like), and a sulfamoyl group (preferably Represents a diethylsulfamoyl group, an octylsulfamoyl group, methyloctadecyl And a sulfone amino group (preferably having a carbon number of 1 to 15 such as a methylsulfonamino group and an octylsulfonamino group).

In the formula (I), TIME is a "timing" group for linking a 1,2,4-triazolyl group to a coupler residue, and is a compound which reacts with the oxidation product of a color developer during the coupling reaction. , 2,4-triazolyl groups are released together with consequent 1,2,4-triazolyl groups during subsequent development. Examples of the timing group represented by TIME in the formula (I) include, for example, the following groups;

Embedded image (Wherein, Z is an oxygen or sulfur atom and is bonded to a coupler, m is 0 or 1, and R ₈ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms or 6 to 6 carbon atoms.
X is a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms,
An alkoxy group, an alkoxycarbonyl group, an acylamino group, an aminocarbonyl group, or the like, or U.S. Pat.
As disclosed in No. 2 gazette,

Embedded image (However, each of the left sides of the above formulas is bonded to a coupler, and Z is an oxygen atom or a sulfur atom or

Embedded image R ₉ , R ₁₀ and R ₁₁ are hydrogen, alkyl or aryl, and Q is U.S. Pat.
As described in JP-A-409,323, it is a 1,2- or 1,4-phenylene group or a naphthylene group. ). )including.
In the formula (I), the alkyl group represented by R ₃ and R ₄ preferably has 1 to 1 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and a tert-butyl group. 4 is a lower alkyl group.

A preferred example of the DIR yellow dye-forming coupler (a) of the present invention is represented by the formula (II).

Embedded image (Wherein R ₃ and R ₄ , TIME and n are the same as defined in the formula (I), R ₆ represents an alkyl group or an aryl group, R ₇ represents a halogen atom,
An alkyl group (having 1 to 20 carbon atoms) or (having 6 to 10 carbon atoms)
And the Ball group are hydrophobic ballast groups. )

In the above formula (II), the alkyl group represented by R ₆ preferably has 3 to 8 carbon atoms, and more preferably is a branched alkyl group (for example, isopropyl, te
an rt-butyl group or a tert-amyl group), and the aryl group represented by R ₆ is preferably a phenyl group (for example, 2-methyl) which may be substituted with an alkyl or alkoxy group having 1 to 5 carbon atoms. 2- or 4-alkylphenyl groups such as phenyl, 2- or 4-alkoxyphenyl groups,
2-methoxyphenyl, 4-isopropoxyphenyl group or butoxyphenyl group). R ₇ is a halogen atom (such as chlorine) or an alkyl or alkoxy group having 1 to 4 carbon atoms (eg, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, methoxy, ethoxy, propoxy, isopropyl Propoxy, n-butoxy and tert-butoxy).

In the above formula (II), "Ball" represents a ballast group, and is, for example, an organic group having a size and a shape such that a bonded group is not diffused from a coating layer in a photographic material. Such a ballast group may be a hydrophobic organic residue having 8 to 32 carbon atoms (e.g., an alkylene group, an imino group, an ether group, a thioether group, a carboxylic group) directly or via a divalent linking group bonded to a coupler. Amide group, sulfonamide group, ureido group, ester group, imide group, carbamoyl group and sulfamoyl group). Specific examples of useful ballast groups are described, for example, in U.S. Patent Nos. 3,337,344; 3,418,129; 4,138,258 and 4.451.559 and British Patent 1,494,777. Na (linear, branched or cyclic)
Alkyl group, alkenyl group, alkylaryl group, alkylaryloxy group, alkylamidoalkyl group, alkoxyalkyl group, alkoxyaryl group, or alkyl group substituted with aryl group or heterocyclic group, substituted with aryloxyalkoxycarbonyl group And a residue containing both an aryl group, an alkenyl group and a long-chain alkenyl-aliphatic group, and a carboxyl group or a water-soluble sulfo group.

Another specific example of a yellow dye forming DIR coupler (a) is represented by formula (III).

Embedded image Wherein R ₃ and R ₄ are as defined in formula (I), TIME and n are also as defined in formula (I), and R ₁₂ is a branched chain Represents an alkyl group, preferably a branched alkyl group having 3 to 8 carbon atoms (for example, an isopropyl group, an isobutyl group, a tert-butyl group or a tert-amyl group), and R ₁₃ preferably has 8 to 22 carbon atoms. An alkyl group (for example, dodecyl group, tetradecyl group, hexadecyl group or octadecyl group), preferably having 10 carbon atoms
To 32 phenoxyalkyl groups (for example, γ- (2,4-diter
t-amylphenoxypropyl) group), preferably carbon number
10-32 alkoxyphenyl groups or preferably carbon number
Represents an aralkyl group of 10 to 32. )

In the present specification, when a “group” is used to represent a compound or a substituent, the chemical substance represented by the “group” includes a basic group, a ring or a residue, and a group having a known substituent. , Ring or residue. Here, when a compound or a substituent is represented by “unit”, it is intended to include only unsubstituted chemical substances. For example, “alkyl group” includes not only alkyl units such as methyl, ethyl, butyl, octyl, stearyl, etc., but also halogen, cyano, hydroxyl, nitro, amino,
Units having a substituent such as carboxylate and the like are also included. On the contrary, the “alkyl unit” indicates only methyl, ethyl, stearyl, cyclohexyl and the like.

The specific yellow dye forming DIR coupler (a) of the formula (I) used in the present invention is illustrated below, but the present invention is not limited thereto.

Embedded image

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Embedded image

In the coupling position used in the present invention,
The yellow dye-forming DIR coupler (a) having a 1,2,4-triazolyl group bonded thereto can be synthesized by a conventional method for preparing a DIR coupler (see, for example, EP 747,763).

The yellow dye-forming malonic acid diamide D of the present invention
The IR coupler (b) is a 4,7-dihalogen-2-benzotriazolyl group bonded via a nitrogen atom to the 2-position carbon of the active methylene group (active coupling position) of the yellow dye-forming coupler. And the remaining 5- and 6-positions of the group may be substituted or unsubstituted.

The yellow dye-forming malonic acid diamide D of the present invention
The IR coupler (b) is represented by the formula (IV).

Embedded image (Wherein, R ₁₄ and R ₁₅ are the same or different and represent a halogen atom (chlorine, bromine, iodine, and fluorine);
And R ₁₆ and R ₁₇ are the same or different and are a hydrogen atom, a halogen atom (chlorine, bromine, iodine and fluorine), an amino group, an alkyl group having 1 to 4 carbon atoms (for example,
A methyl group, an ethyl group, a butyl group, a chloromethyl group, a trifluoromethyl group, a 2-hydroxyethyl group, etc., an alkoxy group having 1 to 4 carbon atoms (for example, a methoxy group, a chloromethoxy group, an ethoxy group, a butoxy group, etc.) ), A hydroxyl group, a cyano group, an aryloxy group (eg, phenoxy group, p-methoxyphenoxy group, etc.), an acyloxy group (eg, acyloxy group, benzoyloxy group, etc.), an acyl group (eg, acyl group, benzoyl group, etc.), alkoxy Carbonyl group (eg, methoxycarbonyl group, butoxycarbonyl group, etc.), aryloxycarbonyl group (eg, benzoxycarbonyl group, etc.), acylamino group (eg, acetamido group, benzamide group, etc.), alkylsulfonyl group (eg, methylsulfonyl) Group, chloromethylsulfonyl group, etc.), aryls Ruphonyl group (eg, phenylsulfonyl group, naphthylsulfonyl group, etc.), alkoxysulfonyl group (eg, ethoxysulfonyl group, butoxysulfonyl group, etc.), aryloxysulfonyl group (eg, phenoxysulfonyl group, 2-methoxyphenoxysulfonyl group, etc.) or an ureido group (e.g., phenyl ureido group, Butan'ureido group), R ₁₈ and R
₁₉ represents an alkyl group (having 1 to 20 carbon atoms) or an aryl group (having 3 to 20 carbon atoms, particularly a phenyl group). )

In the above formula (IV), the alkyl group represented by R ₁₈ and R ₁₉ preferably has 1 to 18 carbon atoms and may be substituted or unsubstituted. Preferred examples of the alkyl group substituent include an alkoxy group, an aryloxy group, a cyano group, an amino group, an acylamino group, a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, and a heterocyclic group. Specific examples of useful alkyl groups are isopropyl, isobutyl, tert-butyl, isoamyl, tert-amyl, 1,1-dimethylbutyl, 1,1-dimethylhexyl, 1,1-
Diethylhexyl, 1,1-dimethyl-1-methoxyphenoxymethyl, 1,1-dimethyl-1-ethylthiomethyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, 2-
Methoxyisopropyl, 2-phenoxypropyl, α-aminoisopropyl, α-succinimidoisopropyl and the like.

In particular, the yellow dye forming DIR malonic diamide coupler (b) of the present invention can be represented by formula (V).

Embedded image Wherein R ₁₆ and R ₁₇ are the same as defined in formula (IV), and R ₂₀ and R ₂₁ are each a hydrogen atom or a halogen atom (chlorine, bromine, iodine and fluorine)
And each of R ₂₂ and R ₂₃ represents a halogen atom, a nitro group, a cyano group, a thiocyano group, a hydroxyl group, an alkoxy group (preferably having 1 to 15 carbon atoms such as a methoxy group, an isopropoxy group, an octyloxy group, and the like). Things),
An aryloxy group (preferably having up to 20 carbon atoms such as phenoxy group, nitrophenoxy and the like), an alkyl group (preferably having 1 to 15 carbon atoms such as methyl group, ethyl group and dodecyl group), An alkenyl group (preferably having 1 to 15 carbon atoms such as an allyl group) and an aryl group (preferably having up to 10 carbon atoms, for example, having 6 to 10 carbon atoms such as a phenyl group, a toluyl group, etc. ), An amino group (for example, an unsubstituted amino group or an alkylamino group having 1 to 15 carbon atoms such as a diethylamino group, an octylamino group, etc.), a carboxyl group, an acyl group (preferably an acetyl group, a decanoyl group) 2 carbon atoms such as
16), alkoxycarbonyl group (where the alkyl unit preferably has 1 to 20 carbon atoms, for example, methoxycarbonyl group, butoxycarbonyl group, octylcarbonyl group, dodecyloxycarbonyl group, 2-methoxyethoxycarbonyl group, etc.) ), An aryloxycarbonyl group (alkyl group preferably having 6 to 20 carbon atoms, such as phenoxycarbonyl group, toluylcarbonyl group, etc.), carbamoyl group (eg, ethylcarbamoyl group, octylcarbamoyl group, etc.), acylamino group (Preferably, an acetamido group, an octaneamido group,
C2-C21 such as tert-pentylphenoxyacetamide group, etc., sulfonyl group, alkylsulfonyl group (preferably C1-C15 such as methylsulfonyl group, octylsulfonyl group, etc.), aryl A sulfonyl group (preferably having 6 to 20 carbon atoms such as a phenylsulfonyl group, an octyloxyphenylsulfonyl group, etc.)
), An alkoxysulfonyl group (preferably having 1 to 15 carbon atoms such as a methoxysulfonyl group, an octyloxysulfonyl group, etc.), an aryloxysulfonyl group (preferably having 6 to 15 carbon atoms such as phenoxysulfonyl, 20), a sulfamoyl group (preferably a carbon atom having 1 carbon atom such as a diethylsulfamoyl group, an octylsulfamoyl group, a methyloctadecylsulfamoyl group, etc.)
To 15), a sulfonamino group (preferably having 1 to 15 carbon atoms such as a methylsulfonamino group and an octylsulfonamino group) and the like. )

The total number of carbon atoms contained in R ₂₂ and R ₂₃ is preferably between 6 and 35.

The yellow dye-forming malonic diamide D of the present invention
The IR coupler (b) can in particular be represented by the formula (VI).

Embedded image (Wherein, R ₂₄ and R ₂₅ each represent an alkyl group having 1 to 20 carbon atoms (eg, a methyl group, an ethyl group, a dodecyl group, etc.), and R ₂₆ and R ₂₇ each represent a C 1 to C 4
(E.g., a methyl group, an ethyl group, a butyl group, etc.). )

Specific examples of the yellow dye-forming malonic diamide DIR coupler (b) used in the present invention are shown below.

Embedded image

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The yellow dye-forming malonic diamide DIR coupler (b) used in the present invention is disclosed in US Pat.
In the same manner as described in 52, it can be synthesized by the following method known for DIR coupler synthesis. The yellow dye-forming malonic diamide DIR coupler (b) used in the present invention may be, for example, a hydrophilic coupler having a water-soluble group such as a carboxyl group, a hydroxyl group or a sulfo group (Fischer-based coupler). It may be a hydrophobic coupler. Methods for adding a coupler to a hydrophilic colloidal solution or to a silver halide gelatin photographic emulsion or dispersing a coupler therein are generally known in the art, for example, a solid dispersion method, a latex dispersion method,
And preferably, an oil dispersion method. For example, the hydrophobic coupler of the present invention can be dissolved in a water-insoluble, high-boiling organic solvent, and the resulting solution is, for example, described in U.S. Pat.
As described in 2,304,939 and 2,322,027, etc., it can be emulsified in an aqueous medium. Or,
The hydrophobic coupler is dissolved in the water-insoluble high-boiling organic solvent in combination with a low-boiling organic solvent, and the resulting solution is prepared, for example, in U.S. Patent Nos. 2,801,170; 2,801,171 and It can be emulsified in an aqueous medium as described in Japanese Patent No. 2,949,360. Typical high boiling known solvents include phthalates (eg, dibutyl phthalate and dioctyl phthalate), phosphates (eg, tricresyl phosphate and trioctyl phosphate) and N-substituted amides (eg, N, N-diethyl lauramide). Typical known low-boiling solvents include ethyl acetate, butyl acetate, methyl ethyl ketone, socrohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like. A specific example of the latex dispersion method is described in U.S. Pat. No. 4,199,363.

DIR coupler (a) used in the present invention
And (b) are preferably incorporated into a silver halide emulsion layer. Preferably, the DIR couplers (a) and (b) are incorporated into a blue-sensitive or sensitized silver halide emulsion layer associated with a yellow dye-forming coupler. More preferably, a yellow dye-forming DIR coupler (a) having a 1,2,4-triazolyl group bonded at a coupling position and a yellow dye-forming malonic diamide DIR coupler (b) of the present invention used in the present invention. Are incorporated into a blue-sensitive silver halide emulsion layer. The preferred amount of yellow dye forming DIR coupler (a) having a 1,2,4-triazolyl group attached at the coupling position is in the range of about 0.010 to about 0.100 g, preferably about 0.020 g / cm ^{2 of} color photographic element.
And the weight ratio to the silver halide in the blue photosensitive layer is from about 0.045 to about 0.090. In contrast, the preferred amount of yellow dye-forming malonic diamide DIR coupler (b) used is in the range of about 0.005 to about 0.040 g, preferably about 0.010 g / cm ^{2 of} color photographic element.
And the weight ratio to silver halide in the blue-sensitive layer is from about 0.020 to about 0.050.

The photographic element of the invention preferably comprises a blue-sensitive or sensitized silver halide layer associated with a yellow dye-forming color coupler, a green sensitized silver halide associated with a magenta dye-forming color coupler. A color multilayer element consisting of a layer and a red sensitized silver halide emulsion layer associated with a cyan dye forming color coupler. Each layer can be comprised of a single emulsion layer or multiple emulsion composite layers sensitive to a particular visible spectral region. If the multilayer material comprises a blue, green or red photosensitive multiple composite layer, it may be a relatively sensitive or insensitive composite layer. The photographic element may contain additional layers such as filter layers, interlayers, protective layers, underlayers, and the like.

"Association" means that the coupler is positioned in association with the silver halide emulsion, and the layers interact to allow the interaction between the silver image formed by development and the colored image formed by the coupler. Refers to the harmonization of image aspects. This is achieved by placing the coupler in a silver halide emulsion layer or in a non-photosensitive colloidal layer adjacent to said emulsion layer. Preferred couplers for use in the present invention are those that do not diffuse due to the presence of a hydrophobic ballast group in the molecule.

The most useful cyan dye-forming couplers are the conventional phenolic and α-naphthol compounds. Examples of cyan couplers are described in U.S. Pat. Nos. 2,369,929; 2,474,293; 2,895,826;
No. 3,311,476; No. 3,253,924; No. 3,419,39
No. 0, No. 3,458.315; No. 3,476,563 and No. 3,591,383; British Patent No. 1,201,110, and Research Disclosure
sclosure) can be selected from among 308119, VII, 1989.

The most useful magenta dye forming couplers are the conventional pyrazolone or indazolone, cyanoacetyl, pyrazolotriazole compounds and the like. Among these, a particularly preferred compound is a pyrazolone coupler. Magenta dye-forming couplers are described, for example, in U.S. Pat. Nos. 2,600,788; 2,983,608; 3,062;
No. 653; No. 3,127,269; No. 3,311,476; No. 3,419,391; No. 3,519,429;
No. 3,558,319; No. 3,582,322; No. 3,615,50
No. 6,834,908 and 3,891,445, and Research Disclosure No. 308119.
VII, 1989.

The silver halide emulsion used in the present invention is a fine dispersion of silver chloride, silver bromide, silver chlorobromide, silver iodobromide and silver chloroiodobromide in a hydrophilic binder. May be. The hydrophilic binder is selected from those commonly used in the photographic art, gelatin;
Gelatin derivatives such as acylated gelatin, grafted gelatin, etc .; albumin; gum arabic; agar; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose, etc .; hydrophilic containing synthetic resins such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, etc. Polymer. Preferred silver halides are silver iodobromide or silver iodobromide chloride containing 1 to 20 mol% of iodide. The silver halide grains may have a cubic, tetradecahedral, columnar-like crystal structure or a combination thereof. Silver halide may have regular grain size or a broader size distribution. Silver halide dimensions can range from about 0.1 to 5 mm.

The silver halide emulsion is a single emulsion.
It may be prepared using a jet method, a double jet method, or a combination of these methods, or may be aged using, for example, an ammonia method, a neutralization method or an acidic method. The emulsion used in the present invention is used for research and
Disclosure 17643, III and IV, December 1978
Month and Research Disclosure Section 308119, II
I, may be chemically and optically sensitized as described in 1989.

The emulsions include optical brighteners, anti-fogging agents, stabilizers, filters and anti-halation dyes, masking dyes, development accelerator releasing couplers, curing agents, coating aids, plasticizers and lubricants, and , Research Disclosure Section 17643, V, V
I, VIII, X, XI and XII, December 1978 and Research
Disclosure Section 308119, V, VI, VIII, X, XI and XII, may contain other additives as described in 1989.

The photographic emulsion layer and the photographic element layer are
For example, Research Disclosure Section 17643, IX,
Various colloids, such as the binders described in December 1978, may be included alone or in combination. The emulsions described above can be coated on various support substrates (cellulose triacetic acid, paper, resin-coated paper, for example, polyesters such as polyethylene terephthalate or polyethylene naphthalate support substrates) on Research Disclosure Section 17643, XV And XVII, December 1978 and Research Disclosure Section 308119, XVI
I, can be applied by utilizing various means as described in 1989. The photosensitive silver halide contained in the photographic element of the present invention is developed after exposure to associate the silver halide with the alkaline aqueous medium in the presence or in the element of the developer contained in the aqueous medium. Thereby, a visible image can be formed. Formulations and methods are described in Research Disclosure Section 17643, XIX, XX and X
XI, December 1978 and Research Disclosure Section 308119, XIX and XX, 1989.

[0040]

The present invention will be described with reference to the following examples.
The present invention is not limited to these. Example 1 A multilayer color photographic element (Sample 101: Control Sample) was prepared by coating layers of the following composition on a transparent cellulose acetate film support having a gelatin underlayer. In the following compositions, the coating amounts of silver halide (expressed in silver equivalent), gelatin and other additives are expressed in g / m ² . All silver halide emulsions were
Stabilized with -6-methyl-1,3,3a, 7-tetraazaindene,
Spectral sensitized with a sensitizing dye suitable for light in the red, green and blue spectra.

First layer (antihalation layer) Black colloidal silver 0.190 Gelatin 1.270 Dye 1 0.023 Dye 2 0.037 Magenta masking coupler MM-1 0.028 Magenta masking coupler MM-2 0.014

Second layer (intermediate layer) Gelatin 1.100 Dye 1 0.016 BARC 0.062 UV-1 0.056 UV-2 0.056 Compound 1 0.051

Third layer (lowest sensitivity red photosensitive layer) Silver iodide bromide emulsion 0.580 (AgI 2.5 mol%, average particle size 0.22 μm) Gelatin 1.180 Cyan coupler C-1 0.280 DIR coupler D-1 0.016 Cyan masking Coupler CM-1 0.007 Dye 1 0.001 Dye 2 0.009

Fourth layer (medium-sensitivity red photosensitive layer) Silver iodide bromide emulsion 0.610 (AgI 6 mol%, average particle size 0.60 μm) Gelatin 0.790 Cyan coupler C-1 0.204 DIR coupler D-1 0.012 Cyan Masking coupler CM-1 0.036 Dye 1 0.001

Fifth layer (highest sensitivity red photosensitive layer) Silver iodide bromide emulsion 0.640 (AgI 12 mol%, average particle size 1.10 μm) Gelatin 0.970 Cyan coupler C-1 0.094 Cyan coupler C-2 0.015 DIR coupler D-1 0.008 Cyan masking coupler CM-1 0.018 Dye 1 0.002

Sixth layer (intermediate layer) Gelatin 1.170 Compound 1 0.070 Hardener H-1 0.074

7th layer (lowest sensitivity green photosensitive layer) Silver iodide bromide emulsion 0.520 (AgI 2.5 mol%, average particle size 0.22 μm) Gelatin 1.160 Magenta coupler M-1 0.311 DIR coupler D-2 0.011 Magenta masking Coupler MM-1 0.016 Magenta masking coupler MM-2 0.008 Compound 1 0.010 Dye 1 0.006

Eighth layer (medium sensitivity green photosensitive layer) Silver iodide bromide emulsion 0.900 (AgI 6.0 mol%, average particle size 0.60 μm) Gelatin 1.300 Magenta coupler M-1 0.089 DIR coupler D-2 0.050 Magenta Masking coupler MM-1 0.038 Magenta masking coupler MM-2 0.019 Compound 1 0.014

Ninth layer (green sensitive layer having the highest sensitivity) Silver iodide bromide emulsion 0.830 (AgI 12.0 mol%, average particle size 1.10 μm) Gelatin 0.970 Magenta coupler M-2 0.150 DIR coupler D-2 0.002 Magenta masking Coupler MM-1 0.026 Magenta masking coupler MM-2 0.013 Compound 1 0.013

Tenth layer (intermediate layer) Gelatin 1.040

Eleventh layer (yellow filter layer) Gelatin 1.040 Yellow colloidal silver 0.056 Hardener H-1 0.065

Twelfth layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion 0.236 (AgI 2.5 mol%, average particle size 0.22 μm) Silver iodide bromide emulsion 0.294 (AgI 6.0 mol%, average particle Gelatin 1.020 Yellow coupler Y-1 0.834 Compound (I-1) of the present invention 0.044

Thirteenth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion 0.460 (AgI 12.0 mol%, average particle size 1.20 μm) Gelatin 0.990 Yellow coupler Y-1 0.231 Compound of the present invention (I- 1) 0.025 Cyan coupler C-2 0.010

Fourteenth layer (first protective layer) Unsensitized silver bromide Lippman emulsion 0.207 Gelatin 1.150 UV-1 0.098 UV-2 0.098 Compound 2 0.134

Fifteenth layer (second protective layer) Gelatin 0.860 Matte polymethyl methacrylate particles 0.014 Ethyl methacrylate-methacrylic acid copolymer 0.175 Matting agent Hardener H-2 0.388

Example 2 Next, instead of the compound I-1 of the present invention, the compound II-
Another color photographic material (hereinafter referred to as Comparative Sample 102) was prepared containing a 13th layer (high-sensitivity blue photosensitive emulsion layer) using the same molar amount of 1 (30 μmol / m ² ). . In addition, other multilayer color photographic materials (hereinafter, referred to as
Call samples 103-107; this is the sample of the present invention)
Also, using the combination of the compounds I-1 and II-1 of the present invention, the first compound was used in the amounts (mg / m ² ) shown in Table 1 below.
It was prepared in the same manner as in Sample 101 of Example 1, except that it was added to the three high-sensitivity blue photosensitive emulsion layers.

A sample of each film was exposed to white light at a color temperature of 5,500 ° K. All exposed samples are standard developer
Using the C41, British Journal of Photography, 1974
Developed as described on July 12, 2008, pp. 597-598.
With respect to the red, green and blue photosensitive layers, the photospeed at optical densities 0.2 and 1.0 higher than the minimum optical density and the particle size of the green photosensitive layer obtained at an optical density of 0.7 were measured, respectively.

[0058]

[Table 1]

From the results shown in Table 1 above, Comparative Samples 101 and 1
02 does not give good results. In fact,
Comparative sample 101 containing compound I-1, but not compound II-1, of the present invention exhibited good photospeed but exhibited too high an unacceptable particle size. Conversely, compound I-1 of the present invention
Rather, Sample 102, containing Compound II-1, exhibited good particle size, but exhibited too low an unacceptable photospeed.

In contrast, the compounds I-1 and II-1 of the present invention
Samples 103-107, which contain both, showed a very good particle size when compared to the values obtained for sample 102, and showed a very slight reduction in speed in all layers. Gave.

The chemical formulas of the compounds used in the above Examples are shown below.

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[0062]

According to the present invention, in at least one blue-sensitive layer associated with a yellow dye-forming coupler, a development inhibitory compound can be released upon reaction with an oxidized product of a developer.
By including two different DIR (development inhibitor releasing) couplers, a better intermediate image effect and better particle size can be obtained, while at the same time suppression of sensitivity degradation can be achieved.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Angelo Tunino, Italy-17016 Ferrania (Savona), within Imation Riccierque Societa per Achioni (72) Inventor Massimo Bertordi Italy, I −17016 Ferrania (Savona), within Imation Richerque Societa per Acioni

Claims (13)

[Claims] 1. a) a yellow dye-forming DIR coupler having a 1,2,4-triazolyl group bonded at the coupling position; and b) a 4,7-dihalogen-2-benzotriazolyl group at the coupling position. Yellow dye-forming malonic acid diamide DI
A light sensitive silver halide color multilayer photographic material comprising a support coated with at least one silver halide emulsion layer containing an R coupler. 2. The yellow dye-forming DIR coupler (a).
The photosensitive halogen according to claim 1, wherein the 1,2,4-triazolyl group is a group having a benzylthio substituent to which a hydrolyzable alkoxy- or aryloxy-carbonyl group is bonded on the 1,2,4-triazolyl group. Silver halide color multilayer photographic material. 3. A yellow dye-forming DIR coupler having a 1,2,4-triazolyl group bonded at the coupling position (a)
Has the formula (I): (Wherein, R ₁ is an alkyl group, an aryl group, or —NHR
₅ group (wherein, R ₅ represents. Alkyl group or an aryl group) represents, R ₂ represents an alkyl group or an aryl group, TIME represents a "timing" group, n is 0 or 1 , R ₃ represents an alkyl group or a phenyl group, and R ₄ represents a hydrogen atom or an alkyl group. The photosensitive silver halide color multilayer photographic material according to claim 1, which is represented by the following formula: 4. A yellow dye-forming DIR coupler having a 1,2,4-triazolyl group bonded at the coupling position (a)
Has the formula (II): (Wherein, R ₃ represents an alkyl group or a phenyl group;
R ₄ represents a halogen atom or an alkyl group;
E represents a “timing” group, n represents 0 or 1, R ₆ represents an alkyl or aryl group, R ₇ represents
Represents a halogen atom, an alkyl group or an aryl group, and the Ball group is a hydrophobic ballast group. The photosensitive silver halide color multilayer photographic material according to claim 1, which is represented by the following formula: 5. A yellow dye-forming DIR coupler (a) having a 1,2,4-triazolyl group bonded at the coupling position.
Has the formula (III): (Wherein, R ₃ represents an alkyl group or a phenyl group;
R ₄ represents a halogen atom or an alkyl group;
E represents a “timing” group, n represents 0 or 1, R ₁₂ represents a branched-chain alkyl group, R ₁₃ represents an alkyl group, a phenoxyalkyl group, an alkoxyphenyl group or an aralkyl group . The photosensitive silver halide color multilayer photographic material according to claim 1, which is represented by the following formula: 6. The yellow dye-forming malonic acid diamide DI
The R coupler (b) has the formula (IV): (Wherein, R ₁₄ and R ₁₅ are the same or different and represent a halogen atom, and R ₁₆ and R ₁₇ are the same or different and are a hydrogen atom, a halogen atom, an amino group, an alkyl group, an alkoxy group, a hydroxyl group , a cyano group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamino group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxysulfonyl group, an aryloxy sulfonyl group, or a ureido group, and R ₁₈ And R ₁₉ each represents an alkyl group or an aryl group.). 7. The yellow dye-forming malonic acid diamide DI
The R coupler (b) has the formula (V): (In the formula, R ₁₆ and R ₁₇ are the same or different and each represents a hydrogen atom, a halogen atom, an amino group, an alkyl group, an alkoxy group, a hydroxyl group, a cyano group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, Roxycarbonyl group, acylamino group, alkylsulfonyl group, arylsulfonyl group, alkoxysulfonyl group,
Represents an aryloxysulfonyl group or a ureido group;
₂₀ and R ₂₁ each represent a hydrogen atom or a halogen atom, and R ₂₂ and R ₂₃ each represent a halogen atom, a nitro group, a cyano group, a thiocyano group, a hydroxyl group, an alkoxy group, an aryloxy group, an alkyl group, an alkenyl group, Aryl group, amino group, carboxyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, acylamino group, sulfonyl group,
It represents an alkylsulfonyl group, an arylsulfonyl group, an alkoxysulfonyl group, an aryloxysulfonyl group, a sulfamoyl group, or a sulfonamino group. The photosensitive silver halide color multilayer photographic material according to claim 1, which is represented by the following formula: 8. The yellow dye-forming malonic acid diamide DI
The R coupler (b) has the formula (VI): (Wherein, R ₂₄ and R ₂₅ each represent an alkyl group having 1 to 20 carbon atoms, and R ₂₆ and R ₂₇ each represent a lower alkyl group having 1 to 4 carbon atoms).
The photosensitive silver halide color multilayer photographic material as described above. 9. A yellow dye-forming DIR coupler (a) having a 1,2,4-triazolyl group bonded at the coupling position.
Is added in an amount of from 0.010 to 0.100 g / m < ² > of the photographic material. 10. The yellow dye-forming malonic acid diamide D
IR coupler (b) is, the photographic material 1m ² per 0.005 to 0.
2. The light-sensitive silver halide color multilayer photographic material according to claim 1, wherein said photographic material is added in an amount of 040 g. 11. A yellow dye-forming DIR coupler (a) having a 1,2,4-triazolyl group bonded at the coupling position.
Is contained in a blue light-sensitive silver halide emulsion layer associated with a yellow dye-forming coupler. 12. The yellow dye-forming malonic diamide D
A light-sensitive silver halide color multilayer photographic material according to claim 1, wherein the IR coupler (b) is included in a blue-sensitive silver halide emulsion layer associated with a yellow dye-forming coupler. 13. A yellow dye-forming DIR coupler (a) having a 1,2,4-triazolyl group bonded at the coupling position.
2. The photosensitive halogen of claim 1 wherein both the yellow dye-forming malonic acid diamide DIR coupler (b) are included in a sensitive blue-sensitive silver halide emulsion layer associated with the yellow dye-forming coupler. Silver halide color multilayer photographic material.